Ballast Water Treatment Systems

ABSTRACT

A ballast water treatment system. Implementations may include an intake screen, a ballast water intake pump coupled to the intake screen, a screen filter coupled to an outlet of the ballast water intake pump, and a multi-cartridge filter system coupled to the screen filter and with one or more ballast tanks. A ballast water dump pump may be coupled with the one or more ballast tanks. The multi-cartridge filter system may include two or more cartridge filters including a quaternary organosilane coating produced from a quaternary ammonium organosilane reagent.

CROSS REFERENCE TO RELATED APPLICATIONS

This document claims the benefit of the filing date of U.S. ProvisionalPatent Application 62/040,348 to William R. Peterson II, et al.,entitled “Ballast Water Treatment Systems,” which was filed on Aug. 21,2014, the disclosure of which is hereby incorporated entirely herein byreference. This document also claims the benefit of the filing date ofU.S. Provisional Patent Application 61/805,477, entitled “StaticMicrobial Fluid Disinfection Utilizing Open Cell Substrates Treated WithOrganosilane Quaternary Ammonium Chloride Compounds” to William R.Peterson II, et al. which was filed on Mar. 26, 2013, the disclosure ofwhich is hereby incorporated entirely herein by reference.

This application is also a continuation application of the earlier U.S.Utility patent application to William R. Peterson II et al., entitled“Ballast Water Treatment Systems,” application Ser. No. 14/832,937,filed Aug. 21, 2015, now pending, which is a continuation-in-partapplication of the earlier U.S. Utility patent application to William R.Peterson II et al., entitled “Static Fluid Disinfecting Systems andRelated Methods,” application Ser. No. 14/226,720, filed Mar. 26, 2014,which issued as U.S. Pat. No. 9,364,572 on Jun. 14, 2016, which was acontinuation-in-part application of the earlier U.S. Utility patentapplication to William R. Peterson II et al., entitled “AntimicrobialQuaternary Ammonium Organosilane Coatings,” application Ser. No.10/850,121, filed May 19, 2004, now abandoned, which claimed the benefitof the filing date of U.S. Provisional Patent Application 60/472,429entitled “Water & Fluids Purification With Bonded Quaternary AmmoniumOrganosilanes,” to William R. Peterson II, which was filed on May 22,2003, the disclosures of each of which are hereby incorporated entirelyherein by reference.

BACKGROUND 1. Technical Field

Aspects of this document relate generally to methods and compositionsfor reducing the number of microorganisms in a liquid using a solidphase carrier coated with a quaternary ammonium organosilane coating.

2. Background Art

Quaternary ammonium organosilanes have been used in a wide variety ofapplications. U.S. Pat. No. 6,613,755 to Peterson II et al. entitled“Antimicrobial Skin Preparations Containing Organosilane Quaternaries,”issued Sep. 2, 2003, the disclosure of which is hereby incorporatedentirely herein by reference, discloses various examples of uses ofquaternary ammonium organosilane compounds that have antimicrobialproperties.

SUMMARY

Implementations of ballast water treatment systems (ballast watermanagement systems) may include: an intake screen adapted to receiveballast water from a body of water surrounding a ship includingmicroorganisms and a ballast water intake pump coupled to the intakescreen and adapted to draw ballast water in through the intake screen. Ascreen filter may be coupled to the ballast water intake pump and may beadapted to perform a screening of the ballast water output by theballast water intake pump. A multi-cartridge filter system may becoupled to the screen filter and with one or more ballast tanksconfigured to be coupled to the ship. A ballast water dump pump may becoupled with the one or more ballast tanks and may be adapted to drawout ballast water stored in the one or more ballast tanks and dischargeit back to the body of water surrounding the ship. The multi-cartridgefilter system may include two or more cartridge filters including aquaternary ammonium organosilane coating produced from a quaternaryammonium organosilane reagent having the formula:

A may be a member independently selected from the group consisting of—OR⁴, substituted or unsubstituted alkyl, substituted or unsubstitutedheteroalkyl, substituted or unsubstituted cycloalkyl, substituted orunsubstituted heterocycloalkyl, substituted or unsubstituted aryl, andsubstituted or unsubstituted heteroaryl; wherein R⁴ may be a memberselected from the group consisting of hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted heteroalkyl,substituted or unsubstituted cycloalkyl, substituted or unsubstitutedheterocycloalkyl, substituted or unsubstituted aryl, and substituted orunsubstituted heteroaryl; R may be substituted or unsubstitutedalkylene; R¹, R², and R³ may be members each independently selected fromthe group consisting of hydrogen, substituted or unsubstituted alkyl,substituted or unsubstituted heteroalkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted heterocycloalkyl, substitutedor unsubstituted aryl; and substituted or unsubstituted heteroaryl; Zmay be a member selected from the group consisting of fluoride,chloride, bromide, iodide, tosylate, hydroxide, sulfate, and phosphate;and n may be 1, 2, or 3.

Implementations of ballast water treatment systems may include one, all,or any of the following:

The body of water including microorganisms may be one of salt water andfresh water.

A recirculation pump may be coupled with the one or more ballast watertanks where the recirculation pump may be coupled with a recirculationfilter including one or more filter cartridges coated with thequaternary organosilane coating. The recirculation pump may be adaptedto draw water from the one or more ballast water tanks through therecirculation filter and back into the one or more ballast water tanks.

The one or more ballast water tanks may further include an open-celledfoam coated with the quaternary organosilane coating.

The open-celled foam may include a material selected from the groupconsisting of polymeric materials, stainless steel, copper, silicon,carbon, and silicon carbide.

The open-celled foam may include a range of pores per inch (PPI) ofbetween 10 PPI and 110 PPI.

The open-celled foam may have a surface area per gram less than asurface area per gram of one of filter sand and zeolite.

A surface of the one or more ballast tanks may be coated with thequaternary organosilane coating.

The quaternary ammonium organosilane reagent includesTetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;Didecylmethyl-N-(3-trimethoxysilylpropyl)ammonium chloride; and anycombination thereof.

Implementations of a ballast water treatment system may include anintake screen adapted to receive ballast water from a body of watersurrounding a ship including microorganisms. A ballast water intake pumpmay be coupled to the intake screen and may be adapted to draw ballastwater in through the intake screen. A screen filter may be coupled to anoutlet of the ballast water intake pump, where the screen filter isadapted to perform a screening of the ballast water output by theballast water intake pump. A multi-cartridge filter system may becoupled with the screen filter and with one or more ballast tanksconfigured to be coupled with the ship. A ballast water dump pump may becoupled with the one or more ballast tanks and may be adapted draw outballast water stored in the one or more ballast tanks and discharge itback to the body of water surrounding the ship. The multi-cartridgefilter system comprises two or more cartridge filters including aquaternary organosilane coating produced from a quaternary ammoniumorganosilane reagent having the formula:

A_(4-n)Si(R NHaR¹ _(b) Z)_(n)

A may be a member selected from the group consisting of alkoxy radicalsof 1 to 8 carbon atoms, alkylether alkoxy radicals of 2 to 10 carbonatoms, and alkyl radicals with 1 to 4 carbon atoms. R may be a divalenthydrocarbon radical with 1 to 8 carbon atoms. R¹ may be a memberselected from the group consisting of alkyl radicals with 1 to 12 carbonatoms, alkyl ether hydrocarbon radicals of 2 to 12 carbon atoms,hydroxy-containing alkyl radicals of 1 to 10 carbon atoms, andnitrogen-containing hydrocarbon radicals of 1 to 10 carbon atoms,wherein the nitrogen atoms has three bonds. The a may be 0, 1, or 2; bmay be 1, 2, or 3; and the sum of a and b may be 3. Z may be a memberselected from the group consisting of chloride, bromide, iodide,tosylate, hydroxide, sulfate, and phosphate. The n may be 1, 2 or 3.

Implementations of ballast water treatment systems may include one, any,or all of the following:

The body of water including microorganisms may be one of salt water andfresh water.

A recirculation pump may be included coupled with the one or moreballast water tanks. The recirculation pump may be coupled with arecirculation filter including one or more filter cartridges coated withthe quaternary organosilane coating. The recirculation pump may beadapted to draw water from the one or more ballast water tanks throughthe recirculation filter and back into the one or more ballast watertanks.

The one or more ballast water tanks may further include an open-celledfoam coated with the quaternary organosilane coating.

The open-celled foam may include a material selected from the groupconsisting of polymeric materials, stainless steel, copper, silicon,carbon, and silicon carbide.

The open-celled foam includes a range of pores per inch (PPI) between 10PPI and 110 PPI.

The open-celled foam may include a surface area per gram less than asurface area per gram of one of filter sand and zeolite.

A surface of the one or more ballast tanks may be coated with thequaternary organosilane coating.

A ballast water treatment system may include an intake screen, a ballastwater intake pump coupled to the intake screen, a screen filter coupledto an outlet of the ballast water intake pump, and a multi-cartridgefilter system coupled to the screen filter and with one or more ballasttanks. A ballast water dump pump may be coupled with the one or moreballast tanks. The multi-cartridge filter system may include two or morecartridge filters including a quaternary organosilane coating producedfrom a quaternary ammonium organosilane reagent having the formula:

A may be a member independently selected from the group consisting of—OR⁴, substituted or unsubstituted alkyl, substituted or unsubstitutedheteroalkyl, substituted or unsubstituted cycloalkyl, substituted orunsubstituted heterocycloalkyl, substituted or unsubstituted aryl, andsubstituted or unsubstituted heteroaryl; wherein R⁴ may be a memberselected from the group consisting of hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted heteroalkyl,substituted or unsubstituted cycloalkyl, substituted or unsubstitutedheterocycloalkyl, substituted or unsubstituted aryl, and substituted orunsubstituted heteroaryl; R may be substituted or unsubstitutedalkylene; R¹, R², and R³ may be members each independently selected fromthe group consisting of hydrogen, substituted or unsubstituted alkyl,substituted or unsubstituted heteroalkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted heterocycloalkyl, substitutedor unsubstituted aryl; and substituted or unsubstituted heteroaryl; Zmay be a member selected from the group consisting of fluoride,chloride, bromide, iodide, tosylate, hydroxide, sulfate, and phosphate;and n may be 1, 2, or 3. The ballast water treatment system may beadapted to receive ballast water via the intake screen from a body ofsea water including microorganisms and achieve at least a 95% reductionin a number of the microorganisms in the ballast water after a singlepass through the multi-cartridge filter system.

The foregoing and other aspects, features, and advantages will beapparent to those artisans of ordinary skill in the art from theDESCRIPTION and DRAWINGS, and from the CLAIMS.

BRIEF DESCRIPTION OF THE DRAWINGS

Implementations will hereinafter be described in conjunction with theappended drawings, where like designations denote like elements, and:

FIG. 1 illustrates the reduction in the viable number of bacteriophagesby quaternary ammonium organosilane coated zeolite;

FIG. 2 illustrates the reduction in the viable number of (A) K. terrienabacteria and (B) E. Coli bacteria by quaternary ammonium organosilanecoated zeolite;

FIG. 3 illustrates the average reduction in the viable number ofbacteria and bacteriophages by quaternary ammonium organosilane coatedzeolite;

FIG. 4 illustrates the reduction in the viable number of algae byquaternary ammonium organosilane coated zeolite;

FIG. 5 illustrates the reduction in the viable number of protozoaparasites by quaternary ammonium organosilane coated zeolite;

FIG. 6 illustrates an experimental apparatus containing a column packedwith quaternary ammonium organosilane coated zeolite for use indecreasing the viable number of microorganisms in a liquid;

FIG. 7 illustrates a block diagram of a first implementation of aballast water management system (BWMS);

FIG. 8 illustrates a block diagram of a second implementation of a BWMS;

FIG. 9 illustrates an exemplary cartridge filter for use in amulti-cartridge filter system.

DESCRIPTION

This disclosure, its aspects and implementations, are not limited to thespecific components, assembly procedures or method elements disclosedherein. Many additional components, assembly procedures and/or methodelements known in the art consistent with the intended static fluiddisinfecting systems and related method implementations will becomeapparent for use with particular implementations from this disclosure.Accordingly, for example, although particular implementations aredisclosed, such implementations and implementing components may compriseany shape, size, style, type, model, version, measurement,concentration, material, quantity, method element, step, and/or the likeas is known in the art for such static fluid disinfecting systems, andimplementing components and methods, consistent with the intendedoperation and methods.

Definitions

As used herein, the term “reducing the viable number of microorganisms,”means reducing the number of microorganisms capable of growing, working,functioning, and/or developing adequately. The term includes, forexample, reducing the overall number of microorganisms, reducing thenumber of active microorganisms (i.e. inactivating microorganisms),reducing the number of microorganisms able to reproduce, reducing thenumber of intact microorganisms, reducing the number of infectiousagents, removal of microorganisms, inactivation of microorganisms;and/or and the like. “Eliminating the viable number of microorganisms”means reducing the viable number of microorganisms to zero.

The term “microorganism,” as used herein, means an organism that,individually, can only be seen through a microscope. The termmicroorganism includes, for example, bacteria, fungi, actinomycetes,algae, protozoa, yeast, germs, ground pearls, nematodes, viruses,prions, and algae.

The abbreviations used herein have their conventional meaning within thechemical and biological arts.

Where chemical groups are specified by their conventional chemicalformulae, written from left to right, they equally encompass thechemically identical substituents that would result from writing thestructure from right to left, e.g., —CH₂O— is equivalent to —OCH₂—.

The term “alkyl,” by itself or as part of another substituent, means,unless otherwise stated, a straight (i.e. unbranched) or branched carbonchain containing at least one carbon, which may be fully saturated,mono- or polyunsaturated. An unsaturated alkyl group is one having oneor more double bonds or triple bonds. An “unsubstituted alkyl” refers tobranched or unbranched alkyl groups wherein the backbone carbons areattached to hydrogen and/or other backbone carbon. The term “alkylene”refers to a divalent radical derivative of an alkyl.

A “backbone carbon” or “backbone heteroatom,” as used herein, refers toa carbon or heteroatom, respectively, that is not at the point ofattachment of an alkyl or heteroalkyl group, and which forms part of abranched or unbranched chain containing at least one carbon.

The term “alkoxy,” refers to those alkyl groups attached to theremainder of the molecule via an oxygen atom.

The term “alkylether” refers to an alkyl having at least onecarbon-oxygen-carbon linkage.

The term “hydroxy-substituted alkyl” refers to an alkyl having at leastone attached hydroxyl group.

The term “amine-substituted alkyl” refers to an alkyl having at leastone attached primary, secondary, or tertiary amine group.

The term “hetero alkyl,” by itself or in combination with another term,means an alkyl having at least one heteroatom within the carbon chain.The heteroatom is selected from the group consisting of O, N, and S,wherein the nitrogen and sulfur atoms may optionally be oxidized and thenitrogen heteroatom may optionally be quaternized. The heteroatom(s) O,N, and S may be placed at any interior position of the heteroalkyl groupor at the position at which the alkyl group is attached to the remainderof the molecule. Up to two heteroatoms may be consecutive, such as, forexample, —CH₂—NH—OCH₃. Similarly, the term “heteroalkylene” by itself oras part of another substituent means a divalent radical derived fromheteroalkyl. For heteroalkylene groups, heteroatoms can also occupyeither or both of the chain termini.

An “unsubstituted heteroalkyl” refers to branched or unbranchedheteroalkyl groups wherein the backbone carbons are attached tohydrogen, other backbone carbons, and/or backbone heteroatoms. Thebackbone heteroatoms are attached to hydrogen, backbone carbons, otherbackbone heteroatoms, and/or oxygen (in the case of oxidized sulfur).

The terms “cycloalkyl” and “heterocycloalkyl,” by themselves or incombination with other terms, represent, unless otherwise stated, cyclicversions of “alkyl” and “heteroalkyl,” respectively. Additionally, forheterocycloalkyl, a heteroatom can occupy the position at which theheterocycle is attached to the remainder of the molecule. The terms“cycloalkylene” and “heterocycloalkylene” refer to the divalentderivatives of cycloalkyl and heterocycloalkyl groups, respectively.

The terms “halo” or “halogen,” by themselves or as part of anothersubstituent, mean, unless otherwise stated, a fluorine, chlorine,bromine, or iodine atom. Additionally, terms such as “haloalkyl,” aremeant to include monohaloalkyl and polyhaloalkyl.

The term “aryl” means, unless otherwise stated, a polyunsaturated,aromatic, hydrocarbon which can be a single ring or multiple rings(preferably from 1 to 3 rings) which are fused together or linkedcovalently. The term “heteroaryl” refers to aryl groups (or rings) thatcontain from one to four heteroatoms selected from N, O, and S, whereinthe heteroatom occupies a ring vertex (also referred to herein as a“ring heteroatom”). The nitrogen and sulfur atoms are optionallyoxidized, and the nitrogen atom(s) are optionally quaternized. Aheteroaryl group can be attached to the remainder of the moleculethrough a carbon or heteroatom. The terms “arylene” and “heteroarylene”refer to the divalent derivatives of aryl and heteroaryl groups,respectively.

An “unsubstituted aryl” or “unsubstituted heteroaryl” refers to aryl andheteroaryl rings, respectively, in which the carbon atoms occupying ringvertices that are not at a point of attachment to the remainder of themolecule are attached only to hydrogen or other atoms occupying ringvertices. Heteroatoms occupying ring vertices that are not at a point ofattachment to the remainder of the molecule are attached only tohydrogen, other atoms occupying ring vertices, or oxygen (in the case ofoxidized ring heteroatoms).

The term “oxo” as used herein means an oxygen that is double bonded to acarbon atom.

A “liquid,” as used herein, is a substance that flows freely, lackscrystal structure, and, unlike a gas, retains the same volumeindependent of the shape of its container at ambient temperature andpressure. An “aqueous liquid” refers to a liquid having a portion ofwater. Aqueous liquids suitable for the practice of the presentinvention include, for example, waste water and sewage water, fruitjuices, milk, and medical fluids. Other suitable fluids will be readilydetermined by those skilled in the art and may be utilized in variousimplementations.

A “solid,” as used herein, is a substance that does not dissolve inwater at ambient temperature. Thus, a “solid phase carrier” is a carrierthat is insoluble in water at ambient temperature.

Methods

In one aspect, the present invention provides a method of reducing oreliminating the viable number of microorganisms in a liquid. The methodincludes contacting the liquid with a solid phase carrier coated with aquaternary ammonium organosilane coating. The quaternary ammoniumorganosilane coating may reduce the viable number of microorganisms in aliquid by directly contacting the microorganisms.

A wide variety of solid phase carriers are useful in conjunction withthe methods and compositions of the present invention. The solid phasecarrier may be any appropriate dimension or shape, including, forexample, a planar surface, the lining of tubing or pipe, or a roughlyspherical particle. The solid phase carrier may also be any appropriatesize, including, for example, a microscopic carrier, a carrierdetectable with the naked eye, a roughly planar carrier with dimensionsthat are centimeters to meters in length, and roughly spherical carrierwith a radius that is centimeters to meters in length.

The solid phase carrier is typically composed of one or more substanceor material that is insoluble in liquid media (e.g. organic media,aqueous media, water, etc.). Exemplary materials include glass, silica,sand (e.g. manganese greensand and filter sand), quartz, flint, zeolite,anthracite, activated carbon, garnet, ilmenite, benn, aluminum(including non-hydrous aluminum silicate (e.g. filter AG), oxides ofiron and titanium (e.g. ilmenite), diatomaceous earth, pozzolan(silicon/alumina material that occurs naturally and is produced as abyproduct of coal combustion), metal (e.g. tin), ceramic, and/or organicpolymers and plastics (e.g. high density polyethylene (HDPE),polypropylene (PP) or polyvinyl chloride (PVC)).

In various implementations, the liquid is contacted with an additionalsolid phase carrier. The additional solid phase carrier may be coatedwith a different quaternary ammonium organosilane coating than the solidphase carrier. The additional solid phase carrier may also be composedof a different material than the solid phase carrier.

Quaternary Ammonium Organosilane Reagents

The solid phase carriers of the current invention are coated with aquaternary ammonium organosilane coating. The quaternary ammoniumorganosilane coating is produced from a quaternary ammonium organosilanereagent. The quaternary ammonium organosilane reagent has the formula:

In Formula (I), A is selected from —OR⁴, substituted or unsubstitutedalkyl, substituted or unsubstituted heteroalkyl, substituted orunsubstituted cycloalkyl, substituted or unsubstituted heterocycloalkyl,substituted or unsubstituted aryl, and substituted or unsubstitutedheteroaryl. Where more than one A is present, each A is independentlyselected from the groups recited above or below.

R⁴ is selected from hydrogen, substituted or unsubstituted alkyl,substituted or unsubstituted heteroalkyl, substituted or unsubstitutedcycloalkyl, substituted or unsubstituted heterocycloalkyl, substitutedor unsubstituted aryl, and substituted or unsubstituted heteroaryl.

R is selected from substituted or unsubstituted alkylene, substituted orunsubstituted heteroalkylene, substituted or unsubstitutedcycloalkylene, substituted or unsubstituted heterocycloalkylene,substituted or unsubstituted arylene, and substituted or unsubstitutedheteroarylene.

R¹, R², and R³ are independently selected from hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted heteroalkyl,substituted or unsubstituted cycloalkyl, substituted or unsubstitutedheterocycloalkyl, substituted or unsubstituted aryl, and substituted orunsubstituted heteroaryl.

Z is selected from fluoride, chloride, bromide, iodide, tosylate,hydroxide, sulfate and phosphate.

The symbol n is 1, 2 or 3.

In an exemplary implementation, each substituted alkyl, substitutedheteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl,substituted aryl, and substituted heteroaryl described herein aspossible A, R¹, R², R³, and R⁴ moieties are substituted only with atleast one substituent independently selected from —OH, unsubstituted(C₁-C₅)alkyl, unsubstituted 2 to 5 membered heteroalkyl, unsubstituted(C₅-C₇) membered cycloalkyl, unsubstituted 5 to 7 memberedheterocycloalkyl, unsubstituted aryl, and unsubstituted heteroaryl. Forexample, where A is a substituted (C₁-C₁₀)alkyl, the substituted(C₁-C₁₀)alkyl is substituted only with at least one substituentindependently selected from —OH, unsubstituted (C₁-C₅)alkyl,unsubstituted 2 to 5 membered heteroalkyl, unsubstituted (C₅-C₇)membered cycloalkyl, unsubstituted 5 to 7 membered heterocycloalkyl,unsubstituted aryl, and unsubstituted heteroaryl.

In other implementations, each substituted alkyl, substitutedheteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl,substituted aryl, and substituted heteroaryl described herein aspossible A, R¹, R², R³, and R⁴ moieties are substituted only with atleast one substituent independently selected from —OH, unsubstituted(C₁-C₅)alkyl, unsubstituted 2 to 5 membered heteroalkyl, unsubstituted(C₅-C₇) membered cycloalkyl, unsubstituted 5 to 7 memberedheterocycloalkyl, unsubstituted aryl, and unsubstituted heteroaryl. Inother implementations, each substituted alkyl, substituted heteroalkyl,substituted cycloalkyl, substituted heterocycloalkyl, substituted aryl,and substituted heteroaryl described herein as possible A, R¹, R², R³,and R⁴ moieties are substituted only with at least one substituentindependently selected from —OH, unsubstituted (C₁-C₅)alkyl,unsubstituted (C₅-C₇) membered cycloalkyl, and unsubstituted phenyl. Inyet other implementations, each substituted alkyl, substitutedheteroalkyl, substituted cycloalkyl, substituted heterocycloalkyl,substituted aryl, and substituted heteroaryl described herein aspossible A, R, R², R³, and R⁴ moieties are substituted only with atleast one unsubstituted (C₁-C₃)alkyl.

In another exemplary embodiment, each substituted alkylene, substitutedheteroalkylene, substituted cycloalkylene, substitutedheterocycloalkylene, substituted arylene, and substituted heteroarylenedescribed herein as possible R moieties are substituted only with atleast one substituent independently selected from —OH, unsubstituted(C₁-C₅)alkyl, unsubstituted 2 to 5 membered heteroalkyl, unsubstituted(C₅-C₇) membered cycloalkyl, substituted 5 to 7 memberedheterocycloalkyl, unsubstituted aryl, and unsubstituted heteroaryl.

In various implementations, each substituted alkylene, substitutedheteroalkylene, substituted cycloalkylene, substitutedheterocycloalkylene, substituted arylene, and substituted heteroarylenedescribed herein as possible R moieties are substituted only with atleast one substituent independently selected from —OH, unsubstituted(C₁-C₅)alkyl, unsubstituted 2 to 5 membered heteroalkyl, unsubstituted(C₅-C₇) membered cycloalkyl, unsubstituted 5 to 7 memberedheterocycloalkyl, unsubstituted aryl, and unsubstituted heteroaryl. Inother implementations, each substituted alkylene, substitutedheteroalkylene, substituted cycloalkylene, substitutedheterocycloalkylene, substituted arylene, and substituted heteroarylenedescribed herein as possible R moieties are substituted only with atleast one substituent independently selected from —OH, unsubstituted(C₁-C₅)alkyl, unsubstituted (C₅-C₇) membered cycloalkyl, andunsubstituted phenyl. In yet other implementations, each substitutedalkylene, substituted heteroalkylene, substituted cycloalkylene,substituted heterocycloalkylene, substituted arylene, and substitutedheteroarylene described herein as possible R moieties are substitutedonly with at least one unsubstituted (C₁-C₃)alkyl.

A may be selected from —OR⁴, substituted or unsubstituted (C₁-C₁₀)alkyl,substituted or unsubstituted 2 to 12 membered heteroalkyl, substitutedor unsubstituted (C₅-C₇)cycloalkyl, substituted or unsubstituted 5 to 7membered heterocycloalkyl, substituted or unsubstituted aryl, andsubstituted or unsubstituted heteroaryl. R⁴ may be selected fromhydrogen, substituted or unsubstituted (C₁-C₁₀)alkyl, substituted orunsubstituted 2 to 10 membered heteroalkyl, substituted or unsubstituted(C₅-C₇)cycloalkyl, substituted or unsubstituted 5 to 7 memberedheterocycloalkyl, substituted or unsubstituted aryl, and substituted orunsubstituted heteroaryl.

In some implementations, A is selected from —OR⁴, unsubstituted(C₁-C₁₀)alkyl, unsubstituted 2 to 12 membered heteroalkyl, unsubstituted(C₅-C₇)cycloalkyl, unsubstituted 5 to 7 membered heterocycloalkyl,unsubstituted aryl, and unsubstituted heteroaryl. In otherimplementations, A is selected from —OR⁴, unsubstituted (C₁-C₁₀)alkyl,unsubstituted 3 to 12 membered alkylether, unsubstituted(C₅-C₇)cycloalkyl, and unsubstituted phenyl.

A may also be selected from —OR⁴, unsubstituted (C¹-C⁴)alkyl,unsubstituted 3 to 8 membered alkylether, unsubstituted(C⁵-C⁷)cycloalkyl, and unsubstituted phenyl. Alternatively, A isselected from —OR⁴, unsubstituted (C₁-C₄)alkyl, and unsubstituted 3 to 8membered alkylether.

R⁴ may be selected from hydrogen, unsubstituted (C₁-C₁₀)alkyl,unsubstituted 2 to 12 membered heteroalkyl, unsubstituted(C₅-C₇)cycloalkyl, unsubstituted 5 to 7 membered heterocycloalkyl,unsubstituted aryl, and unsubstituted heteroaryl.

In some implementations, R⁴ is selected from hydrogen, unsubstituted(C₁-C₁₀)alkyl, unsubstituted 3 to 12 membered alkylether, unsubstituted(C₅-C₇)cycloalkyl, and unsubstituted phenyl. In a related embodiment, R⁴is selected from hydrogen, unsubstituted (C₁-C₅)alkyl, unsubstituted 3to 8 membered alkyl ether, unsubstituted (C₅-C₇)cycloalkyl, andunsubstituted phenyl. Alternatively, R⁴ is selected from hydrogen,unsubstituted (C₁-C₅)alkyl, and unsubstituted 3 to 8 membered alkylether.

R⁴ may also be selected from phenyl, methylphenyl, substituted orunsubstituted (C₁-C₅)alkyl, and —(CH₂)_(x)—O—(CH₂)_(y)CH₃. X and y areintegers independently selected from 1 to 10.

R may be selected from substituted or unsubstituted (C₁-C₁₀) alkylene,substituted or unsubstituted 2 to 10 membered heteroalkylene,substituted or unsubstituted (C₅-C₇)cycloalkylene, substituted orunsubstituted 2 to 7 membered heterocycloalkylene, substituted orunsubstituted arylene, and substituted or unsubstituted heteroarylene.

In various implementations, R is a member selected from unsubstituted(C₁-C₁₀)alkylene, unsubstituted 2 to 10 membered heteroalkylene,unsubstituted (C₅-C₇)cycloalkylene, unsubstituted 5 to 7 memberedheterocycloalkylene, unsubstituted arylene, and unsubstitutedheteroarylene.

R may also be unsubstituted (C₁-C₁₀)alkylene.

R¹, R², and R³ may be selected from hydrogen, substituted orunsubstituted (C₁-C₂₀)alkyl, substituted or unsubstituted 2 to 20membered heteroalkyl, substituted or unsubstituted (C₅-C₇)cycloalkyl,substituted or unsubstituted 5 to 7 membered heterocycloalkyl,substituted or unsubstituted aryl, and substituted or unsubstitutedheteroaryl.

In some implementations, R, R², and R³ are independently selected fromhydrogen, unsubstituted (C₁-C₂₀)alkyl, hydroxy-substituted(C₁-C₂₀)alkyl, amine-substituted (C₁-C₂₀)alkyl, unsubstituted 2 to 20membered heteroalkyl, unsubstituted (C₅-C₇)cycloalkyl, unsubstituted 5to 7 membered heterocycloalkyl, unsubstituted aryl, and unsubstitutedheteroaryl. In a related embodiment, R¹, R², and R³ are independentlyselected from hydrogen, unsubstituted (C₁-C₂₀)alkyl, unsubstitutedalkylether, hydroxy-substituted (C₁-C₂₀)alkyl, amine-substituted(C₁-C₂₀)alkyl, unsubstituted (C₅-C₇)cycloalkyl, and unsubstitutedphenyl.

R¹, R², and R³ may also be selected from hydrogen, unsubstituted(C₁-C₂₀)alkyl, unsubstituted alkylether, hydroxy-substituted(C₁-C₂₀)alkyl, amine-substituted (C₁-C₂₀)alkyl, unsubstituted(C₅-C₇)cycloalkyl, and unsubstituted phenyl. Alternatively, R¹, R², andR³ are selected from hydrogen, unsubstituted (C₁-C₂₀)alkyl,unsubstituted alkylether, hydroxy-substituted (C₁-C₂₀)alkyl, andamine-substituted (C₁-C₂₀)alkyl.

In other exemplary embodiments, R¹, R², and R³ are independentlyselected from —(CH₂)_(q)OCH₃, —(CH₂)_(q)OH, —(CH₂)_(q)O(CH₂)_(t)CH₃,—(CH₂)_(q)NHCH₃, —(CH₂)_(q)NH₂, —(CH₂)_(q)N(CH₃)₂ and—(CH₂)_(q)NH₂(CH₂)_(t)CH₃, in which q and t are integers independentlyselected from 0 to 10. R¹, R², and R³ may also be independently selectedfrom the group consisting of —CH₂CH₂OCH₃ and —CH₂CH₂OCH₂CH₂CH₃.Alternatively, R¹, R², and R³ may also be independently selected from—CH₂CH₂OH and —CH₂CH₂CH₂CH(OH)CH₃. R¹, R², and R³ may also beindependently selected from —CH₂CH₂NH₂ and —CH₂CH₂N(CH₃)₂. Finally, R¹,R², and R³ may be members independently selected from methyl, octadecyl,didecyl, and tetradecyl.

In an exemplary embodiment, the quaternary ammonium organosilane reagentis selected from (CH₃O)₃Si(CH₂)₃N+(CH₃)₂(C₁₈H₃₇) (Cl⁻);(CH₃CH₂O)₃Si(CH₂)₃N+(CH₃)₂(C₁₈H₃₇) (Cl⁻);(CH₃O)₃Si(CH₂)₃N+(CH₃)₂(C₁₈H₃₇) (Br⁻); (CH₃O)₃Si(CH₂)₃N+(C₁₀H₂₁)₂(CH₃)(Cl⁻); (CH₃O)₃Si(CH₂)₃N+(CH₃)₂(C₁₄H₂₉) (Cl⁻);(CH₃O)₃Si(CH₂)₃N+(CH₃)₂(C₁₄H₂₉) (Br⁻); and(CH₃O)₃Si(CH₂)₃N+(CH₃)₂(C₁₆H₃₃) (Cl⁻). In a related embodiment, thequaternary ammonium organosilane reagent is selected from3-(trimethoxysilyl)propyldimethyloctadecyl ammonium chloride,3-(trimethoxysilyl)propyldidecylmethyl ammonium chloride, and3-(trimethoxysilyl)propyldimethyltetradecyl ammonium chloride.

In another exemplary embodiment, the quaternary ammonium organosilanecontains an ammonium halide and a hydrolyzable alkoxy group bonded tosilicon.

Quaternary Ammonium Organosilane Coatings

A variety of methods may be used to form the quaternary ammoniumorganosilane coatings from quaternary ammonium organosilane reagents.The quaternary ammonium organosilane reagent may be applied to the solidphase carrier using any method known in the art, including, for example,methods for covalently or non-covalently binding the quaternary ammoniumorganosilane reagent to the solid phase carrier to form a quaternaryammonium organosilane coating.

Solid phase carriers may be contacted (e.g. sprayed, dipped, orotherwise applied) with a solution preparation containing the quaternaryammonium organosilane reagent. In some embodiments, the quaternaryammonium organosilane reagent coated surfaces are allowed to air dry atroom temperatures for a sufficient period of time to complete acondensation cure of the quaternary ammonium organosilane coating.Alternatively, heat is applied to the coated surfaces for a sufficientperiod of time to effect cure, the duration and temperature of such isknown to those skilled in the art.

In various implementations, the quaternary ammonium organosilane reagentis covalently bound to the solid phase carrier. Typically, thequaternary ammonium organosilane reagent is covalently bound to anaccessible carrier reactive group that forms a part of the solid phasecarrier. A variety of reactive groups are useful in covalently bindingthe quaternary ammonium organosilane reagent. The quaternary ammoniumorganosilane reagent may be covalently bound to the carrier reactivegroup through the silane moiety of the quaternary ammonium organosilanereagent. The silane moiety, as used herein, refers to theA_(4-n)-Si-portion of the compound Formula I.

The silane moiety may be covalently bound to the carrier reactive groupby allowing the carrier reactive group to covalently bind to the siliconatom of the silane moiety. For example, where the carrier reactive groupis a hydroxyl, the oxygen atom may be allowed to bind to the siliconatom to form a silicon-oxygen bond thereby covalently attaching thequaternary ammonium organosilane reagent to the carrier molecule. In arelated embodiment, the silane moiety includes at least one —OR⁴ thatleaves upon attack of a hydroxyl carrier reactive group. This reactionmay be referred to herein as a condensation reaction. Thus, thequaternary ammonium organosilane reagent may be covalently attached tothe carrier molecule via a condensation reaction.

The silane moiety may also include an A group that contains a reactivegroup, referred to herein as a silane reactive group. The silanereactive group is capable of reacting with a carrier reactive group toform a covalent bond.

Silane reactive groups, carrier reactive groups and classes of reactionsuseful in covalently attaching quaternary ammonium organosilane reagentsto a solid phase carrier are generally those that are well known in theart of bioconjugate chemistry. These include, but are not limited tonucleophilic substitutions (e.g. reactions of amines and alcohols withacyl halides, active esters), electrophilic substitutions (e.g., enaminereactions) and additions to carbon-carbon and carbon-heteroatom multiplebonds (e.g., Michael reaction, Diels-Alder addition). These and otheruseful reactions are discussed in, for example, March, Advanced OrganicChemistry, 3rd Ed., John Wiley & Sons, New York, 1985; Hermanson,Bioconjugate Techniques, Academic Press, San Diego, 1996; and Feeney etal., Modification Of Proteins; Advances in Chemistry Series, Vol. 198,American Chemical Society, Washington, D.C., 1982 the disclosures ofwhich are hereby incorporated herein entirely by reference.

Useful silane and carrier reactive functional groups include, forexample:

(a) carboxyl groups and various derivatives thereof including, but notlimited to, N-hydroxysuccinimide esters, N-hydroxybenztriazole esters,acid halides, acyl imidazoles, thioesters, p-nitrophenyl esters, alkyl,alkenyl, alkynyl and aromatic esters;

(b) hydroxyl groups which can be converted to esters, ethers, aldehydes,etc.;

(c) haloalkyl groups wherein the halide can be later displaced with anucleophilic group such as, for example, an amine, a carboxylate anion,thiol anion, carbanion, or an alkoxide ion, thereby resulting in thecovalent attachment of a new group at the site of the halogen atom;

(d) dienophile groups which are capable of participating in Diels-Alderreactions such as, for example, maleimido groups;

(e) aldehyde or ketone groups such that subsequent derivatization ispossible via formation of carbonyl derivatives such as, for example,imines, hydrazones, semicarbazones or oximes, or via such mechanisms asGrignard addition or alkyllithium addition;

(f) sulfonyl halide groups for subsequent reaction with amines, forexample, to form sulfonamides;

(g) thiol groups, which can be converted to disulfides or reacted withacyl halides;

(h) amine or sulfhydryl groups, which can be, for example, acylated,alkylated or oxidized;

(i) alkenes, which can undergo, for example, cycloadditions, acylation,Michael addition, etc.;

(j) epoxides, which can react with, for example, amines and hydroxylcompounds; and

(k) phosphoramidites and other standard functional groups useful innucleic acid synthesis.

The reactive functional groups can be chosen such that they do notparticipate in, or interfere with, the reactions necessary to assemblethe quaternary ammonium organosilane coating. Alternatively, a silane orcarrier reactive functional group can be protected from participating inthe reaction by the presence of a protecting group. Those of skill inthe art will understand how to protect a particular functional groupfrom interfering with a chosen set of reaction conditions. For examplesof useful protecting groups, See Greene et al, Protective Groups InOrganic Synthesis, John Wiley & Sons, New York, 1991, the disclosure ofwhich is incorporated entirely herein by reference.

Linkers may also be employed to attach the quaternary ammoniumorganosilane reagent to the solid phase carrier. Linkers may includereactive groups at the point of attachment to the quaternary ammoniumorganosilane reagent and/or the solid phase carrier. Any appropriatelinker may be used in the present invention, including substituted orunsubstituted alkylene, substituted or unsubstituted heteroalkylene,substituted or unsubstituted cycloalkylene, substituted or unsubstitutedheterocycloalkylene, substituted or unsubstituted arylene, andsubstituted or unsubstituted heteroarylene. In an exemplary embodiment,the linker group is selected from substituted or unsubstituted alkylene,and substituted or unsubstituted heteroalkylene. In a relatedembodiment, the linker is selected from unsubstituted alkylene, alkylenesubstituted with at least one oxy, unsubstituted heteroalkylene, andheteroalkylene substituted with at least one oxy. In another relatedembodiment, the linker is selected from unsubstituted (C₁-C₂₅) alkylene,(C₁-C₂₅) alkylene substituted with at least one oxy, unsubstituted 2 to26 membered heteroalkylene, and 2 to 26 membered heteroalkylenesubstituted with at least one oxy.

Other useful linkers include those having a polyester backbone (e.g.polyethylene glycol), and derivatives thereof. A wide variety of usefullinkers are commercially available (e.g. polyethylene glycol basedlinkers such as those available from Nektar, Inc. of Huntsville, Ala.).

The quaternary ammonium organosilane reagent may also be non-covalentlyattached to the solid phase carrier using any interaction, such as Vander Waals interactions, hydrophobic interactions, dipole-dipoleinteractions, electrostatic interactions, and/or hydrogen bondinginteractions.

In an exemplary embodiment, the quaternary ammonium organosilane reagentforms a polymeric network that partially or wholly covers the solidphase carrier. Where the quaternary ammonium organosilane reagent formsa polymeric network, the quaternary ammonium organosilane reagent mayadditionally from a covalent and/or non-covalent bond with the solidphase carrier.

The quaternary ammonium organosilane reagent typically forms a polymericnetwork by covalently binding through the silane moiety. Where thesilane moiety includes at least one —OR⁴ group, the quaternary ammoniumorganosilane reagent may form a silicone polymer having a series ofsilicon-oxygen-silicon bonds. The silicones may be linear polymers orcross-linked polymers. For example, where the silane moiety includes atleast two —OR⁴ groups, the quaternary ammonium organosilane reagent mayform a cross-linked silicone polymer wherein each silica atom forms partof at least two silicon-oxygen-silicon bonds. Thus, polymerization maybe achieved using silane reactive groups capable of formingintermolecular covalent bonds with other silane reactive groups.

In an exemplary embodiment, the quaternary ammonium organosilane reagentis contacted with an aqueous liquid prior to application to the solidphase carrier. As discussed above, useful quaternary ammoniumorganosilane reagents include those containing hydrolyzable alkoxygroups bound to the silicon atom. Upon contact with a water molecule,the alkoxy groups (e.g. methoxy) may hydrolyze to form hydroxysubstituted silicon atoms (also referred to herein as “silanols”) withsimultaneous liberation of alcohol as a by-product of the hydrolysis(also referred to herein as condensation). The resultant compound formedon addition of quaternary ammonium organosilanes of the abovecompositions are the corresponding mono-, di-, or tri-silanol species.The reactive silanol species prepared upon hydrolysis may form covalentsilicon-oxygen-silicon bonds with other silanol species resulting inpolymeric coatings as described above. The resultant polymeric coatingmay be a molecular network non-covalently and/or covalently bonded tothe solid phase carrier.

It will be understood by those skilled in the art that the quaternaryammonium organosilane coating may form three dimensional, cross-linked,water-insoluble, polymeric coatings which may contain some uncondensedsilanol or alkoxy moieties. Monomeric, dimeric and oligomeric speciesmay be present on the solid phase carrier following application of anaqueous solution containing quaternary ammonium organosilane reagent,and these may bond to the solid phase carrier, whether by covalent ornon-covalent mechanisms.

The quaternary ammonium organosilane coatings formed on the solid phasecarriers retain their antimicrobial activity. They are substantive tothe solid phase carriers and largely insoluble in aqueous liquid. Forexample, in some embodiments, less than 10 ppb of quaternary ammoniumorganosilane reagents is detectable in water after Standard 42 testingas performed by NSF International, Ann Arbor, Mich.

In an exemplary embodiment, the quaternary ammonium organosilane coatinghas the formula:

In Formula II, A, R, R¹, R², and R³ are as defined above in Formula I. Wis a solid phase carrier as described above. The solid phase carrier Wmay include a linker moiety and/or the remnant of a reactive group. Thesymbol 1 represents an integer selected from 1, 2, or 3. The symbols mand j represent integers independently selected from 0, 1, 2, and 3,wherein both m and j are not simultaneously 0. The sum of m, j, and 1 isnot greater than four. In a related embodiment, 1 is 1, 2, or 3; m is 1,2, or 3, and j is 1, 2, or 3. In another related embodiment, 1 is 1; mis 1, 2, or 3, and j is 1, 2, or 3.

Microorganisms

The term “microorganism,” as used herein, means an organism that,individually, can only be seen through a microscope. The termmicroorganism includes, for example, bacteria, fungi, actinomycetes,algae, protozoa, yeast, germs, ground pearls, nematodes, viruses,prions, and algae. Thus, in an exemplary embodiment, the microorganismis selected from bacteria, viruses (also referred to herein asbacteriophages), fungi, algae, mold, yeast, spores, and protozoaparasites. The term “bacteria” includes both gram positive and gramnegative bacteria.

Gram positive bacteria include, for example, Bacillus sp. (vegetativecell), Corynebacterium diptheriae, Micrococcus lutea, Micrococcus sp.,Mycobacterium tuberculosis, Mycobacterium smegmatis, Propionibacteriumacnes, Staphylococcus aureus, Staphylococcus epidermidis, Streptococcusfaecalis, Streptococcus mutans, Streptococcus pneumonia, andStreptococcus pyogenes.

Gram negative bacteria include, for example, Acinetobactercalcoaceticus, Aeromonas hydrophilia, Citrobacter deversus, Citrobacterfeundi, Enterobacter aerogenes, Enterobacter aglomera, Escherichia coli,Klebsiella oxytoca, Klebsiella pneumoniae, Klebsiella terriena,Legionella pneumophila, Morganella morganii, Proteus mirabilis, Proteusvulgaris, Pseudomonas aeruginosa, Pseudomonas fluorscens, Salmonellacholera suis, Salmonella typhi, Salmonella typhimurium, Serratialiquifaciens, and Xanthomonas campestris.

Viruses include, for example, Adenovirus Type II & IV, Bovine AdenovirusType I & IV, Feline pneumonitis, Herpes Simplex Type I, Herpes SimplexType II, HIV-1 (AIDS), Influenza A2 (Aichi), Influenza A2 (Asian),Influenza B, Mumps, Parinfluenza (Sendai), Reovirus Type I, Simian Virus40, Vaccinia, MS2, T2 (non-enveloped virus) and PRD1.

Fungi, algae, mold, yeast, and spores include, for example, Alteraniaalternate, Aspergillus flavus, Aspergillus niger. Aspergillus sydowii,Aspergillus terreus, Aspergillus versicolor, Aspergillus verrucaria,Aureobasidium pullans, Candida albicans, Candida pseudotropocalis,Chaetomium globsum, Cladosporium cladosporioides, Chlorella vulgaris,Dreschslera australiensis, Epidermophyton sp., Gliomasta cerealis,Gloeophyllum trabeum, Microsporum sp., Microsporum audouinii, Moniliagrisea, Oscillatoria, Penicillium chrysogenum, Pencillium commune,Penicillium funiculosum, Penicillium pinophiliumm, Penicillium variable,Phoma fimeti, Pithomyces chartarum, Poria placenta, Scenedesmus,Saccharonyces cerevisiae, Scolecobasidium humicola, Trichoderma viride,Trichophyton interdigitale, Trichophyton maidson, Trichophytonmentogrophytes, and Trichophyton sp.

Protozoa parasites include, for example, Cryptosporidium parvum(oocysts) and Giardia.

For more detailed information regarding antimicrobial activity againstgram positive bacteria, gram negative bacteria, viruses, fungi, algae,mold, yeast, spores and protozoa parasites, see Hsiao, Y. Chinese Pat.Appl., PCT/CN98/00207 (1998); Malek, J. et at., U.S. Pat. No. 4,259,103(1981); Klein, S., U.S. Pat. No. 4,394,378 (1983); Eudy, W., U.S. Pat.No. 4,406,892 (1983); Gettings, R. et al., U.S. Pat. No. 4,908,355(1990) and U.S. Pat. No. 5,013,459 (1991); Blank, L. et al., U.S. Pat.No. 5,145,596 (1992); Avery, R. U.S. Pat. No. 5,411,585 (1995); Blank,L. et al., U.S. Pat. No. 4,865,844 (1989); Battice, D. et al., U.S. Pat.No. 4,631,297 (1986); Higgs, B. et al., U.S. Pat. No. 5,359,104 (1994);Avery, R et al., U.S. Pat. No. 5,411,585 (1995); White, W. et al., Bookof Papers, 12th Annual Nonwovens Tech. Symposium, pp. 13-46 (1984);McGee, J. et al, Am. Dyestuff Rep. 6: 56-59 (1983); Dow CorningTechnical Brochure; 22-994-83 (1983); Gettings, R. et al., Book ofPapers, American Association of Textile Chemists and Colorists NationalTechnical Conference, pp. 259-261 (1978); Dow Corning TechnicalBrochure, 24-095-85 (1985); Tsao, I. et al., Biotechnol. Bioeng., 34:639-46 (1989); Tsao, I et al., ACS Symp. Ser. 419: 250-67 (1990); Klein,M. et al, Principles of Viral Inactivation, 3^(rd) Ed., S. Block, Ed.,(Lea & Febiger, Philadelphia, Pa.) pp. 422-434 (1983); Peterson, W. etal, U.S. Pat. No. 6,613,755; each of which is incorporated entirely byreference herein.

Conventional quaternary ammonium organosilanes are available as 42%active material in methanol under the trademark DOW CORNING® 5700(3-(trimethoxy-silyl)propyldimethyloctadecyl ammonium chloride) by AegisEnvironmental Management, Inc. of Midland, Mich. and Requat 1977(3-(trimethoxysilyl)-propyldidecylmethyl ammonium chloride) by SanitizedInc. of New Preston, Conn. Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (Cat. No. SI06620.0) as a 60% active solution inmethanol, tetradecyldimethyl(3-tri-methoxysilylpropyl) ammonium chloride(Cat. No. SIT7090.0) as a 50% solution in methanol anddidecylmethyl(3-trimethoxysilylpropyl) ammonium chloride (Cat. No.SID3392.0) as a 42% solution in methanol are offered by Gelest, Inc. ofTullytown, P A. They are often applied from solvent solutions such aslower alcohols.

EXAMPLES

The following examples are provided by way of illustration only and notby way of limitation. Those of skill in the art will readily recognize avariety of non-critical parameters that can be changed or modified toyield similar results.

ODTA: Octadecyldimethyl(3-trimethoxysilyl)propyl ammonium chloride.Obtained from Wright Chemical Corp., Wilmington, N.C. as a 42% activematerial in methanol. This material may also be named as3-(trimethoxysilyl)propyl-dimethyloctadecyl ammonium chloride. Alsoavailable as a 42% active material from Aegis Environmental Management,Inc., Midland, Mich. marketed as DOW CORNING® 5700.

REQUAT: 3-(trimethoxysilyl)propyldidecylmethyl ammonium chloride.Obtained from Sanitized Inc., New Preston, Conn.; Requat 1977 as a 42%active material in methanol.

TDTA: 3-(trimethoxysilyl)propyltetradecyldimethyl ammonium chlorideobtained from Gelest, Inc., Tullytown, P A, Cat. No. SIT7090.0 as a 50%solution in methanol.

Example 1

A solution suitable for application was prepared by adding 4 parts ODTAto 100 parts deionized water with stirring. The resulting clear solutionwas applied to an open, polyvinyl chloride (PVC) flat-type evaporationpan by atomized spray, insuring that all surfaces were thoroughlywetted. The pan is allowed to air dry for 24 hours to cure thequaternary ammonium organosilane reagents to the container surface toform a quaternary ammonium organosilane coating. Water containingbacteria level previously measured at 10⁷ total bacteria/ml using aBIOSPERSE® Test Kit was added to the pan in a ratio of 4.6 grams ofwater per square inch of surface area. After 30 minutes the water issampled using a BIOSPERSE® test kit. After incubation, 10⁵ bacteria/mlwas measured. Resampling of the test water at 1 hour and 4 hours gavebacterial counts of 10⁴ and <10³, respectively.

Example 2

A 4 oz. solution prepared according to Example 1 was added to a 1 pinttin-plated metal test container having ¾ inch screw top. The solutionwas agitated to completely wet the inside surface of the container for 1minute and then decanted. The test container was allowed to air dry forone hour. Residual vapors were removed by an air purge for 5 minutes andthe container was then heated to 105° C. for one hour to cure thequaternary ammonium organosilane reagents to the container surface toform a quaternary ammonium organosilane coating. Water (300 g) having ahigh bacterial count of 10⁷ bacteria/ml was added to the test container.The test container was allowed to stand one hour at room temperature.After two hours, the test water bacterial level was measured at 10³bacteria/ml using a BIOSPERSE® test kit.

Example 3

Two ounce containers of glass, high density polyethylene (HDPE),polypropylene (PP) or polyvinyl chloride (PVC) were treated with anaqueous solution containing 1.5% TDTA. The containers were heated to 100C for one hour to cure the quaternary ammonium organosilane reagent tothe container surfaces to form a quaternary ammonium organosilanecoating. Each container was then rinsed with one oz. of deionized water.One ounce of water containing 10⁵ bacteria/ml was added to eachcontainer and capped. After 24 hours at room temperature, each containerwas sampled and bacteria measured with a BIOSPERSE® test kit. Allcontainers indicated bacteria counts of 10³ bacteria/ml followingincubation for 24 hours.

Example 4

Coiled aluminum test tubing 8 ft. in length and having an internaldiameter of ¼ inch was treated with a solution of 8 parts REQUAT to 100parts isopropanol. The tube was filled with the solution, sealed andallowed to stand for 15 minutes. The tube was drained and air dried witha stream of compressed air passing through the tube at a rate of 100ml/minute for 24 hours to cure the quaternary ammonium organosilanereagent to the tubing surfaces to form a quaternary ammoniumorganosilane coating. An aqueous liquid containing 10⁷ units/ml ofbacteria and algae was passed through the coiled aluminum tubing. Theaqueous liquid was gravity circulated through the tubing at a rate of 5ml/minute resulting in contamination of <10³ bacteria/ml.

Example 5

An antimicrobial solution suitable for treatment of silicaeous surfacesincluding sand and zeolites was prepared by adding 67.5 grams REQUAT toa stirred solution containing 3.375 kg deionized water and 3 grams of3-aminopropyltrimethoxysilane. One kg of the clear solution was sprayedonto 50 pounds of #20 white silica pool filter sand over 5 minutes in arotary mixer. The wetted material was mixed with agitation for anadditional hour and allowed to air dry 24 hrs to cure the quaternaryammonium organosilane reagent to the sand surface to form a quaternaryammonium organosilane coating. The treated sand was employed in arecirculating water system to reduce microbial contamination from 10⁷bacteria/ml to <10³ bacteria/ml in 30 minutes of operation as measuredby a BIOSPERSE® test kit.

Example 6

Zeolites containing approximately 90% clinoptilolite (Ash MeadowsZeolites, LLC) of 20-40 mesh were thoroughly wetted with a solutioncontaining 7 parts ODTA and 93 parts water. The wet zeolites wereallowed to air dry 24 hours and then heated 2 hours at 110° C. in aforced air oven to cure the quaternary ammonium organosilane reagent tothe zeolite surfaces to form a quaternary ammonium organosilane coating.The treated zeolites were placed in a 2 inch PVC pipe having an overalllength of 38 inches. As described below, dechlorinated water containingknown quantities of bacteriophages, bacteria, algae and protozoa werepassed through the PVC pipe containing the quaternary ammoniumorganosilane coated zeolites.

The experimental apparatus consisted of a set of three filters (filter1, 2 and 3) attached to a manifold, which included fittings for hoseconnections, and sample ports at the inlet and outlet for each filter(see FIG. 6). An inline mixer was included in the pipe assembly beforeinlet port to maximize microbial monodispersity. The challenge testwater was pumped into each filter at a flow rate of 330 ml/min using athermally protected pump.

Prior to each microbial challenge, the filters were flushed for 25minutes with dechlorinated tap water. The flush water was dechlorinatedusing granular activated carbon filter and chlorine residual wasmeasured before and after the dechlorination using Hach method 8167.

The challenge test water was prepared by adding known number ofmicroorganisms into 20 liters of dechlorinated tap water in apolypropylene container (Nalgene, Rochester, N.Y.). Microbes were washedwith 1× phosphate buffered saline just before spiking in the container.The challenge test water container was placed on a stir plate with aTeflon coated stir bar and continuously mixed to provide homogenousdistribution of microbes in the influent water. The challenge test waterwas pumped into each filter using a thermally protected pump (LittleGiant Potent Pump, Okla. City, Okla.). The pump was primed prior to useby recirculating the microbial stock solution. The hose was connected tothe inlet fitting of each filter. The pump was operated for twelveminutes for each filter. The flow rate was measured using a 1000 mlgraduated cylinder and adjusted to 330 ml/min as recommended by CSL.Based on the hydraulic parameters of the system, each filter needed a12-minute-run to stabilize. The effluent samples were taken from eachfilter after twelve minutes and a single influent sample was collectedfrom the second filter after eight minutes, which represented influentconcentration for the complete run. Once the experiment was complete,the filters were again flushed for 30 minutes with dechlorinated tapwater.

Example 6.1 Bacteriophages

A series of experiments were conducted with the bacteriophages MS2 andPRD1. The effluent and influent samples were taken and diluted asdescribed above. The samples for MS2 and PRD1 were serially diluted andassayed using their respective bacterial hosts by double layer agarmethod (Adams, M. H., Bacteriophages, Interscience, New York (1959)).The plates were incubated at 37 C for 24 hours, at which time clearvirus plaques were counted. The results are presented in FIG. 1. The logremoval and inactivation for MS2 and PRD1 ranged between 2.40 to 2.96,and 1.50 to 2.27 log, respectively. The over average removal for MS2 andPRD1 were 2.8 and 2.0 log, respectively. The data shows that quaternaryammonium organosilane coated zeolite can reduce the viable number ofbacteriophages in aqueous liquid.

Example 6.2 Bacteria

An independent series of experiments were conducted with the bacteriaKlebsiella terriena and E. Coli (ATCC 25922). The effluent and influentsamples were taken and diluted as described above. The samples wereassayed by membrane filtration techniques using 0.4 m pore size membranefilter. The membrane filter was placed on a selective medium andincubated at 37 C for 24 hours, at which time bacterial colonies werecounted. The results are presented in FIGS. 2(A) and (B). As shown inFIG. 2(A) and FIG. 3, consistent removal for Klebsiella was observed inall the filters, which ranged from 99.37% (2.2 log) to 99.60% (2.4 log)with an average of 99.50% (2.3 log). As shown in FIG. 2(B), the removalfor E. coli ranged from 99.96% (3.50 log) to 99.99% (4.39 log) with anaverage of 99.98% (3.88 log). This study shows that quaternary ammoniumorganosilane coated zeolite can effectively reduce the viable numberbacteria in aqueous liquid.

Example 6.3 Algae

Experiments were conducted with Chorella vulgaris to determine both theremoval as well as inactivation effects of the media against algae. Theeffluent and influent samples were taken and diluted as described above.The samples were concentrated by centrifugation before assaying fortotal removal and inactivation. Removal was determined by totalvolumetric counts under microscope. The inactivation rate was determinedby viability test. The algal cells were digested with 2% trypsin (inhanks balanced salt solution) and stained with Fluorescein Diacetate(Sigma Chemicals F-7378). Fluorescein Diacetate (FDA) is a non-polarester that passes through cell membranes. Once inside the cell, FDA ishydrolyzed by esterases (an enzyme present in viable cells) to producefluorescein, which accumulates inside viable cell walls and fluoresceunder UV light. A microscope equipped with both white and ultravioletlight, was used to quantify live and dead algal cells. The results arepresented in FIG. 4. The average removal of 99.11% (2.05 log), 98.74%(1.90 log) and 98.74% (1.90 log) were observed for filter 1, 2, and 3,respectively. The average of three inactivation measurements for filter1, 2, and 3 were 11% (0.05%), 12% (0.06 log) and 22% (0.11 log),respectively. However, based on individual measurements the overallrange of inactivation for the three filters was 5% (0.02 log) to 46%(0.27 log) and averaged at 15% (0.07 log). It is clear that quaternaryammonium organosilane coated zeolite can effectively reduce the viablenumber of algae in aqueous liquid.

Example 6.4 Protozoa Parasites

Cryptosporidium parvum oocysts were obtained from the SterlingParasitology Laboratory at the University of Arizona, Tucson, Ariz., andwere used to determine the efficacy of removal or inactivation ofinfectious oocysts. The removal of Cryptosporidium parvum oocysts wasdetermined by Hemacytometer counts on concentrated samples, whereas, thenumber of infectious oocysts were determined by infection foci detectionmethod using cell culture technique with the most-probable-number assay(FDM-MPN) (Slifko et al., Applied Environmental Microbiology,65:3936-3941 (1999)). The results are presented in FIG. 5.

The cumulative removal/inactivation of infectious C. parvum oocystsaveraged at 97.9% (1.68 log) for all three filters. The removal andinactivation performance by each filter were 95.4% (1.34 log), 99.3%(2.15 log), and 98.9% (1.96 log) for filters 1, 2, and 3, respectively.The removal (only) of oocysts averaged at 71.3% (0.54 log) with anindividual removal of 75.9% (0.62 log), 65.5% (0.46 log), and 72.4%(0.56) for filters 1, 2, and 3, respectively. The study indicates thatquaternary ammonium organosilane coated zeolite can effectively reducethe viable number pf protozoa parasites in aqueous liquid.

Open Cell Substrates

Various implementations of static fluid disinfecting systems my utilizeopen-cell (reticulated) foams (both synthetic and natural). Inparticular implementations, by non-limiting example, the open-cell foam(foam) is composed of one or more cells with structures of, bynon-limiting example, tetrakaihedral, fullerene (“bucky-ball”),dodecahedron, tetrakaidecahedron, Weaire-Phelan structures, honeycomb,bitruncated cubic honeycomb (Kelvin structure), octahedral, anycombination of the foregoing, and any other polyhedral shape.Implementations utilizing Weaire-Phelan structures may incorporate anyof the structures disclosed in D. Weaire et al., “A Counter-Example toKelvin's Conjecture on Minimal Surfaces,” Phil. Mag. Let. 69:107-110(1994), the disclosure of which is incorporated herein entirely byreference. The open-cell foams form an interconnected network of solidstruts. In particular implementations, the foam cells are arranged likesoap suds, forming a three dimensional, packed array of similarly sizedbubble-like structures. These structures may have theoretically maximumvolume and minimal surface area for a given volume. When filled withliquid, the resulting structure is similar to an interpenetratingnetwork of polymers.

Foams containing any of the above structures are available in a varietyof pore structures as measured in pores per inch (PPI). In variousimplementations, the pore size in PPI may range from about 10 to about110. In particular implementations, the pore size may be about 20 toabout 40 PPI. In other implementations, the pore size may be 30 PPI andlower. It has been observed that, as the pore size decreases above 110PPI that the speed and effectiveness of the disinfection decreases. Invarious open-cell foam materials such as natural open cell foammaterials such as sponges, the actual cell size may vary significantlythroughout the material (they may have an average PPI within this rangesabove), but will also perform in this application following treatmentwith organosilane quaternary compounds. In various implementations, theopen-cell foams are compressible structures and will conform to theshape of the container when suitably sized. In particularimplementations, the foam will displace less than about 5% of the liquidvolume enclosed in a container when the foam is dimensioned to fillsubstantially the entire volume of the container. After treatment withorganosilane quaternary compounds, the treated foam may be compressed toless than about 25% of their original volume without observable loss ofantimicrobial activity.

Foams utilized in implementations of static fluid disinfecting systemsdisclosed herein may be made of materials including plastics, polymericmaterials, stainless steel, copper, silicon, carbon and silicon carbide.In particular implementation, the plastic foams may be composed ofvirgin or recycled polyethylene terephthalate (PET),polymethylmethacrylate (PMMA). In various implementations carbon foamsmay compose at least a portion of activated carbon. In implementationswhere the foam is made of a metallic, semi-metallic, or compositematerial, the foam may take the form of a mesh structure. Where thefoams are made of polyethylene and other plastic materials, they may bethose manufactured by New England Foam Products, LLC of Hartford, Conn.In various implementations where the foam takes the form of a mesh, themesh treated with organosilane quaternary compounds could also bearranged in a three dimensional shape like a mechanical stirring device.

Implementations of antimicrobial foams like those disclosed herein areprepared by applying an aqueous or alcoholic solution containing about0.1% to about 5.0% by weight of an organosilane quaternary ammoniumhalide compound to the foam substrate by immersion, pressure spray,electrostatic spray methods, and other methods disclosed in thisdocument. The wetted foams are allowed to air dry or are heated toapproximately 120 C to complete curing of the antimicrobial film to thesurfaces of the foam cells. When dried/cured, the surface of the foamcell structures contains a substantially uniform film of theorganosilane material bonded to the surface through silsesquioxane-likestructures. The resultant bonded film is insoluble in water and commonsolvents and is not removed or leached off during operation in aqueousenvironments. The coverage of the bonded film on the structure of thefoam can be evaluated visually by performing a blue dye test usingbromophenol blue. The test is carried out by applying a quantity ofbromophenol blue solution to the foam, and after allowing the solutionto rest on the foam for about 30 seconds, washing the bromophenol bluesolution out of the foam. The portions of the structure of the foam thatretain the blue color are those that contain bonded film, as thebromophenol blue couples to the organosilane material and not to thefoam material.

In various implementations, the organosilane quaternary compound usedfor treating may be octadecyldimethyl-(3-trihydroxsilylypropyl) ammoniumchloride. In other implementations, organosilane starting materials forformation of films may include one, all, or any of the following:

Octadecyldimethyl-(3-methoxysilyslpropyl)ammonium chloride:C₁₈H₃₅(CH₃)₂N⁺(CH₃O)₃SiC₃H₇ Cl⁻

Tetradecyldimethyl-(3-trimethoxysilylpropyl)ammonium chloride:C₁₄H₂₉(CH₃)₂N+(CH₃O)₃SiC₃H₇ Cl⁻

Didecylmethyl-(3-trimethoxysilylpropyl)ammonium chloride(C₁₀H₂₁)₂CH₃N+(CH₃O)₃SiC₃H₇ Cl⁻

In various implementations, other substrate reactive organosilanesincluding ammonium chloride moieties may be utilized. Any of theorganosilane compounds disclosed in this document may be employed invarious implementations.

In this document, filter media treated with organosilane quaternaryammonium materials are disclosed that remove pathogens from waterpassing through the filter media of 2 log for bacteria and up to 98% forparasitic protozoa such as Cryptosporidium parvum. It was previouslytheorized that the increased surface area of a media, especially in thecase of filter media such as sand or zeolites, would result in increasedelimination and inactivation of pathogens dispersed in the water. Thefoams disclosed herein have a greatly reduced surface area (less than orequal to about 1 m²/gram) when compared with filter media such as filtersand (tens of m²/gram) or zeolites (hundreds of m²/gram), but alsodemonstrate significant antimicrobial activity when placed in a staticcontainer of liquid sufficient to disinfect the fluid. The open-cellfoams have a minimal surface area as the foam, during manufacture, seeksto create a maximum volume with a minimum surface area and resultingsurface energy (driven by surface tension and surface free energyeffects).

It has been observed that organosilane quaternary treated foamsmanufactured according the principles in this disclosure eliminate andinactivate bacterial, viral and parasitic protozoa pathogens up to 6 login 10 minutes of static exposure of the pathogen containing liquid tothe submerged foam in a container for an effective period of time. Suchfoams treated with organosilane quaternary compounds have beendemonstrated to rapidly and effectively disinfect fluids in which theyare in contact by inactivating and eliminating a wide variety ofpathogens including viruses (encapsulated and non-encapsulated), algae,gram positive bacteria, gram negative bacteria and parasitic protozoaincluding Cryptosporidium parvum and Giardia. Similar to the otherantimicrobial compounds disclosed herein, the disinfection process isnon-leaching and imparts no detectable antimicrobial agent or compoundsinto the contacting fluid. An example of the performance of animplementation of a treated foam is found below:

Example 7

Twenty samples of water containing bacteria, viruses, andCryptosporidium oocytes were treated according to the standards in theNSF International P248 test for Military Operations MicrobiologicalWater Purifiers. Passage of the test requires that within a maximum of20 minutes for all 20 samples, the bacterial population decrease by 6log, the viral population decrease by 4 log, and the Cryptosporidiumoocytes be reduced by 3 log. When foams treated with 1-Octadecanaminium,N,N-dimethyl-N-(3-(trimethoxysilyl)propyl)-chloride were placed in thetwenty samples, remaining in static contact with the water, in 10minutes 18 of the 20 samples met the test criteria, and by 15 minutes,all 20 samples had experienced microbe reduction to the desired testinglevels. In this case, the effective period of time was reached whenresidual microorganism levels in all the samples reached the desiredreduced level, in 15 minutes.

Unlike the use of treated filter media discussed earlier in thisdocument, the disinfection process occurs under static conditions oflittle to no fluid flow over the treated surface of the foam and isaccordingly not a filtration process for pathogen removal. Because thefoams are suitable for use in non-flowing, fluid conditions they may beuseful for antimicrobial stabilization of fluids for extended periods incontainers. Fluids in contact with treated foams may be stored forextended periods without microbial growth or the need for externalinfluences such as refrigeration. Because of this, implementations oftreated foams like those disclosed herein may be incorporated in fluidtransport vehicles, such as milk tanker trailers, and other bulkfoodstuff transport vehicles and systems. An additional benefit forvehicles like milk tanker trailers is that if the foams are attached atregular intervals along the internal circumference of the tank with adimension extending radially into the milk payload, they will have abaffling effect, reducing momentum flow effects of the milk movingaround during transport. However, because the foams are antimicrobial,the problems of trying to clean a conventional tank with metal bafflesmay be eliminated. In some implementations, gravity fed flow filtrationusing treated foams may be used, provided it is carried out at lowpressures that do not mechanically harm the films.

This result of increased efficacy of the open-cell treated substratewhen compared with the performance of organosilane treated filter mediais unexpected. This is because the surface area of foam media contactingthe contaminated fluid is far less than filter media. For example, thesurface area per volume of the foam implementations when compared withthe surface of zeolite and sand is millions of times smaller. Forexample, the surface area of a zeolite ranges in the hundreds of squaremeters per gram. In contrast, a treated foam with a surface area of just36.4 square feet can disinfect a water bladder that holds 2.5 liters ofwater. This disinfection using foams takes place rapidly (90 seconds-15minutes) compared to previous systems that involved coating the interiorsurface of a bottle with organosilane materials (3 hours). Being able toobtain orders of magnitude improved inactivation or similar inactivationof microbes as with use of treated filter media from a foam with ordersof magnitude less surface area employed in a non-forced flow, staticfluid operating condition is an unexpected result which runs contrary toconventional knowledge of those of ordinary skill in the art.

Once prepared by coating with organosilane quaternary ammoniumcompounds, the treated foams can be stored outside liquid for greaterthan 5 years and still retain their antimicrobial activity. Because ofthis, the effective antimicrobial lifetime of a treated foam isdetermined by the ability of the particular underlying foam material towithstand prolonged exposure to the fluid without beginning to shed orotherwise breakdown mechanically within the fluid. This means that thelimit to the volume of liquid that could be potentially treated by acoated foam is the mechanical lifetime/stability of the foam.

Implementations of foams like those disclosed herein are capable ofdisinfection of clear and turbid water as well as visually opaque fluidsincluding food juices, plant extracts, milk, and milk products. Thesefoams may be particularly useful for visually opaque fluids asconventional methods of fluid disinfection include widespread use ofenergy intensive ultraviolet (UV) radiation for which the fluid must betransparent. Because the foams do not require adding any liquid matterto the liquid or leach into the fluid, they contrast with otherconventional methods which require the addition of toxic, fluid solublecompounds including energy intensive and toxic ozone or equally toxic,carcinogen-producing chlorine, iodine, chlorine dioxide and chloramines.Implementations of foams like these disclosed may be used to disinfectcutting or fracking fluids (hydrocarbon [oil] and water mixtures) aswell as any other flowable liquid that does not contain particulatesthat would clog the foam. Implementations of foams like those disclosedherein may also be employed to disinfect solid materials, such aspowders that are dispersable and can contact the foam. In otherimplementations, implementations of the foams may be used to providedisinfection of solids and liquids through surface contact. For example,in meat packaging, the meat may be laid down on a piece of treated foam(which may be the packaging container in particular implementations),which will act to kill microbes in the meat and in liquids associatedwith the meat during transport and storage prior to food preparation. Insuch implementations, one or more surface of the meat (or other solid)are contacted by the foam.

Implementations of static fluid disinfecting systems employing open-cellfoams like those disclosed herein may employ various implementations ofa method of disinfecting a fluid. Implementations of the method includestatically contacting a fluid containing one or more microorganisms witha foam coated with any one of the quaternary organosilanes disclosedherein in a container that encloses the foam and holds the fluid. Thefluid may contain one or more of any of the microorganisms disclosedherein. In various implementations of the method, the method may includestatically contacting one or more surfaces of a solid included in thecontainer with the foam. This solid could be any disclosed in thisdocument, including foodstuffs and other solid materials that containone or more microorganisms.

Implementations of ballast water treatment systems are disclosed in thisdocument. Ballast water treatment systems are used in ships and vesselstraveling via water that retain or store water for stabilization asballast.

In 2004, the International Convention for the Control and Management ofShips' Ballast Water and Sediments (the Convention) was adopted and hasbeen ratified by sufficient states to go into effect in 2016. TheConvention includes basic standards controlling the amount of harmfulaquatic organisms and pathogens found in ballast water that may bereleased by a ship of any size. The ballast water is taken up typicallyat the beginning of a ship's voyage to a new port and, accordingly, iscomposed of those aquatic organisms and pathogens that are present inthe water in the port of origin. When reaching the destination, releaseof some or all of the stored ballast water is generally done as part ofpreparation of the ship for its next voyage. Since the ship is now atits port of destination, the aquatic organisms present in the ballastwater are potentially not native to that area. Since these non-nativeaquatic organisms enter the environment of the port of destinationseparate from their natural predators, they can rapidly become aninvasive species and destroy the ecological variety of the destinationport. Zebra mussels are an example of a non-native, invasive speciesthat has traveled to North America through ballast water.

A summary of the Convention standards is found in Appendix C of the U.S.

Provisional Patent Application 62/040,348 to William R. Peterson II, etal., entitled “Ballast Water Treatment Systems,” which was filed on Aug.21, 2014 (the '348 Provisional), the disclosure of which was previouslyincorporated entirely herein by reference. To reach these standards fordischarged ballast water from the ship at the port of destination,various conventional ballast water treatment systems have been devised.In the United States, regulations regarding management of ballast waterand associated penalties may be found in 33 C.F.R. §151.1500 et. seq.(2012) and the regulations regarding the approval of ballast watermanagement systems (BWMS) may be found in 46 C.F.R. §162.060 et seq.(2012) the disclosures of which are incorporated entirely herein byreference.

Various implementation of BWMS using quaternary ammonium organosilanecompounds are disclosed in this document. Referring to FIG. 7, animplementation of a BWMS 2 is illustrated that utilizing quaternaryammonium organosilanes to destroy microorganisms in ballast water. Asshown, water (whether fresh or sea water) for use as ballast waterenters through an intake screen, being drawn in through the main ballastwater intake pump. The water then is passed passes through one or morescreen filters (varying sizes of screens may be used). The ballast wateris then passed through one or more multi-cartridge filter devices (inseries or parallel) containing cartridges (cartridge filters) thatcontain quaternary ammonium organosilane coatings. The resultingfiltered ballast water then enters the ballast tank (one or more ballasttanks may be used, located various places on a ship or vessel).

Depending upon the antimicrobial performance of the BWMS, in someimplementations, the filtered sea water may be sufficiently filteredand/or purified to be stored and subsequently released from the ballasttanks following one pass through the one or more multi-cartridge filterswithout requiring further treatment to meet the regulatory standardsdisclosed. In other implementations, while the filtered sea water isresiding in the one or more ballast tanks, the filtered sea water isdrawn into a recirculation loop through use of one or more recirculationpumps and into one or more recirculation filters containing one or morecartridges treated to form a coating of quaternary ammoniumorganosilanes on the material of the one or more cartridges. Therecirculated water then circulates back into the one or more ballasttanks. When changes in the amount ballast water in the ballast tanksneed to be made, water from the ballast tanks is drawn out using theballast water dump pump and discharged into the ambient sea watersurrounding the ship. As required by various regulations, the crew ofthe ship will have completed testing of the ballast water in the ballasttanks to determine the organism and pathogen levels prior to dischargingany of the water.

The foregoing high level review of the process shows the overall flow ofsea water into and out of the ballast tanks. Various implementations ofthe system will employ various filtration, intake, and pumpingcomponents to perform the various functions of the system. Varioussystem implementations operate identically using fresh water as in seawater.

In various implementations, and for the exemplary purposes of thisdisclosure, the intake screen may be any of the self-cleaning suctionscreens disclosed in Appendix E of the '348 Provisional manufactured byVAF Filtration Systems of Arvada, Colo. Many other intake screen designsmay be utilized in various implementations which are adapted to suchfactors as the required volume of water, the cleanliness of the seawater surrounding the vessel, and the size of the intake piping. In theimplementations disclosed in Appendix E, the interior of the screen iswashed continuously using rotating water jets while intake water isbeing simultaneously drawn into the screen preventing particles frombetween about 710 microns to about 1680 microns from being able to enterwith the intake water.

The one or more screen filters for processing the intake sea water maybe, in various implementations, any of the LPV-Series automatic screenfilters manufactured by VAF Filtration Systems of Arvada, Colo. Thesescreen filters permit filtration of matter and organisms down to 80microns at varying flow rate while allowing for cleaning of the filteredmaterial from the filter without stopping of the operation of the screenfilter system. The filter material drawn from the screen filter can be,in various implementations, discharged directly into the watersurrounding the vessel, as the filtered organisms are the same as thosein the intake water and no contamination issues exist with theseorganisms. While in various implementations, screen filters could beused, in others, other passive or automatic filtration systems could beemployed, including, by non-limiting example, membrane, sand, zeolite,and other filter media systems. In all implementations, one or morefilter screens/membranes/stages may be included in each filter, and,where more than one filter is used, they may be arranged to treat theintake water in parallel or in series or in series/parallel combinationsas desired.

Intake water leaving the screen filter is then processed by amulti-cartridge filter system containing many cartridges (cartridgefilters) that have been treated with quaternary ammonium organosilanesto form a coating on the material of filters. A wide variety of filtersystems capable of including multiple cartridges may be included invarious systems implementations. For the exemplary purposes of thisdisclosure, the multi-cartridge systems disclosed in Appendix G of the'348 Provisional manufactured by HARMSCO Filtration Products of NorthPalm Beach, Fla. may be used in particular implementations. Appendix Galso discloses examples of filter cartridge types that may be treatedand used to filter the intake water. Referring to FIG. 9, an example offilter cartridge that can be treated with quaternary ammoniumorganosilanes is illustrated (see also those in Appendix H of the '348Provisional). In various implementations, many different filter types(wound filters, sand filters, zeolite filters, etc.) may be treated withquaternary ammonium organosilanes and placed in a multi-cartridge systemlike those in disclosed in Appendix G (or other systems) and used forfiltration. Various combinations of different filters types may be alsoused in the same multi-filter cartridge filter system. Bag filters mayalso be employed in particular implementations. The systems inillustrated in Appendix G of the '348 Provisional may have improvedfiltration characteristics because they employ cyclonic movement of thewater within the filter vessel over and through the plurality of filtercartridges contained therein.

A wide variety of quaternary ammonium organosilane compounds may beemployed in various implementations of ballast water treatment systemslike those disclosed herein. For example, the compounds could be any ofthose disclosed in this document and in any of the referencesincorporated by reference herein, including the '348 Provisional.

Particular implementations of systems may utilize any one or anycombination of the following quaternary ammonium organosilanes:Tetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride (CAS No.41591-87-1); Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride(CAS No. 27668-52-6); andDidecylmethyl-N-(3-trimethoxysilylpropyl)ammonium chloride (CAS No.68959-20-6). Implementations of various systems may employ quaternaryammonium organosilanes which may include silanes represented by theformula:

A_(4-n)Si(R NHaR¹ _(b) Z)_(n)

A, R, a, n, R¹, b, and z may be any chemical structural moiety (element)identified by the same notation in U.S. Pat. No. 6,613,755 to William R.Petersen II et al., entitled “Antimicrobial skin preparations containingorganosilane quaternaries,” filed Mar. 29, 2002 and issued Sep. 2, 2003,the disclosure of which is incorporated entirely herein by reference.Furthermore, implementations of various ballast water treatment systemsmay employ quaternary ammonium organosilanes which may include silanesrepresented by the formula:

In these implementations, A, n, R, R¹, R², R³, and Z may be any chemicalstructural moiety identified by the same notation in the '121 utility,'429 provisional, the '720 utility, and the '348 Provisional.

Any of the methods of treating filter media, filter cartridges, anddisinfecting foams disclosed in the '121 utility, '429 provisional, '720utility, the '477 provisional, and the '348 provisional with quaternaryammonium organosilane compounds may be employed to treat the filtercartridges and/or filter media included in the filter cartridges thatare included in the multi-cartridge filter system and form a coatingthereon. As disclosed in the foregoing applications, the quaternaryorganosilane compounds are non-leaching, meaning that there is nodetectable active agent present in water leaving the filters. The lifespan of the coating of quaternary ammonium organosilane compound on thefilter media may be about 5 years.

The filters employed may filter pathogens and organisms sized from about0.2 microns to about 25 microns to about 50 microns. In particularimplementations, the filters may be about 3-4 inches in diameter andabout 40 inches long. In other implementations, the filters may be about3 inches long. Depending upon the amount of intake water needing to beprocessed, the number of filters included in the multi-cartridge systemmay be just a few to greater than 160 filters. In variousimplementations, cartridge filters like those disclosed herein may notbe used, but the multi-cartridge filter system may be adapted for usingtreated filter sand, treated zeolite, or other treated filter media thathas been treated to form a coated quaternary organosilane coating likeany of those disclosed in this document and the references incorporatedherein using any reagent disclosed therein. In other implementations, acombination of cartridge filter(s) and treated filter sand, treatedzeolite, or other treated filter media coated with a quaternaryorganosilane coating like those disclosed herein may also be used. Anyof the treated filter sand, treated zeolite, or other treated filtermedia disclosed in this document any in any of the referencesincorporated herein by reference may be used in various implementations.

As disclosed and discussed at length in the '348 provisional and thereferences incorporated herein by reference, as the effectiveness of thequaternary ammonium organosilane compounds for killing and/ordeactivating viruses, bacteria, cysts, spores, yeasts, fungus, eggs, andother microscopic organisms and pathogens is very high, in ballast watertreatment systems like those disclosed herein, the intake water may becleaned to at least the regulatory standards in Appendix C of the '348provisional after just a single pass through the multi-cartridge filtersystem. Accordingly, the water entering the ballast tanks could beimmediately discharged following testing without requiring anyadditional filtration.

Since the filtered water in the ballast tanks has the potential toremain in the tanks for an extended period of time during variousvoyages, the use of a recirculation loop as illustrated FIGS. 7 and 8 asan aid in maintaining the filtered water in the ballast tanks at thedesired cleanliness standard may be important in various systemimplementations. In such systems, the recirculation system can operatecontinuously or periodically on a desired interval, using therecirculation pump to draw water from the ballast tanks and pass itthrough the recirculation filter. In various implementations, therecirculation filter may be a multi-cartridge filter system (thoughsized proportionally smaller to the lower flow), may be a single filtersystem, or a series and/or parallel set of two or more filters. Any ofthe multi-cartridge filter systems disclosed herein may be employed invarious implementations.

In particular implementations of the system, in addition to the filtercartridges and/or filter media being treated with quaternary ammoniumorganosilane compounds, the other components of the system that contactthe ballast water may also be coated with a layer of quaternary ammoniumorganosilanes. Depending upon the implementation, the intake screencomponents, pumps and pump impellers, interior components of the screenfilter, the water-contacting surfaces of the multi-cartridge filtersystem and recirculation filter, all piping, and the interior surfacesof the ballast tanks (walls, floors, or any surface and/or anycombination of surfaces thereof) can be coated with a layer ofquaternary ammonium organosilane compounds like those selected herein.Any of the coating techniques disclosed in any of the referencesincorporated by reference herein may be employed. Also, in variousimplementations, the quaternary ammonium organosilane compound precursormaterials may be applied to the desired surfaces of the various systemcomponents using electrostatic spraying to prevent domain formationbehavior and beading of the film. In particular implementations, tworounds of spraying may be carried out following which a curing processis employed to transition the precursor material sprayed from amonomeric material to self-assembling layers to form a fully curedsilsesquioxane (organosilsesquioxane) structured film. Following use ofthe system, the various system components may need the film reappliedperiodically to keep the film actively able to kill and destroyorganisms and pathogens. Because the various system components may alsobe treated with the quaternary ammonium organosilane compounds, severalbeneficial effects may exist, including the elimination/minimization ofthe formation of biofilms in various parts of the system which createsources of continuous contamination and making it easier to treat andmaintain the ballast water at the desired cleanliness standards.

Implementations of ballast water management systems like those disclosedherein may be employed in a wide variety of watercraft including thosesubject to the regulations in the Convention and those which are not.Implementations of the system may be used for both fresh and marine(salt water) applications, and may, in various system implementations,be equally successful in both fresh and marine applications withoutrequiring any operational changes. Smaller systems may be included inwater craft that operate in fresh waters only and which do not includeballast tanks, but take on water during normal operation or duringstorage at a dock in the form of bilge water. Because of the single passkill capabilities of the systems disclosed herein employing quaternaryammonium organosilanes, such smaller systems may be developed to treatbilge water at the time it is released. Because of this, regulations forsmaller craft that currently require draining and drying beforetransferring the smaller craft from one body of water to another may beunnecessary, as the system is capable of treating any bilge waterreleased from the vessel in the new body of water sufficiently toeliminate the pathogens/organisms present in the bilge water that camefrom the previous body of water.

Furthermore, in various ballast water management systems, staticdisinfection systems and methods like those described in the '720utility, and the '477 provisional may be employed. For example, insmaller ships where the ballast tanks are small, there may not be muchspace for piping for a recirculation loop. Accordingly, the ballasttanks could be at least partially filled with/contain an open-celledfoam material coated with the quaternary ammonium organosilane compoundsand, while the ballast water resides in the ballast tanks, staticdisinfection using the foam may take place as disclosed in thereferences incorporated herein by reference. An implementation of such aballast water management system is illustrated in FIG. 8, which shows aballast tank partially filled with a static disinfecting foam incombination with a recirculation loop. However, in otherimplementations, the recirculation loop may not be included due tosize/complexity restrictions and/or may not be needed in view of thepresence of the foam.

Furthermore, in system implementations that do not employ arecirculation loop, the system may be designed to pass the ballast waterback through the multi-cartridge filter system for a second pass priorto being discharged. A wide variety of system implementations arepossible using the principles disclosed herein, including variousrecycle, multiple pass, recirculation systems that filter betweenballast tanks, and others. Those of ordinary skill in the art willreadily be able to construct system implementations using the principlesdisclosed herein.

Example 7

A sample of the marine salt water (Pacific Ocean, San Diego Bay, Calif.)was used with a test apparatus to determine microbial reductionutilizing treated cartridge filter systems. The test apparatus consistedof stainless steel and PVC piping 0.75 inches in diameter. Pumpingthrough the system was accomplished utilizing an air-actuated diaphragmpump with an adjusted flow rate of 1-2 gallons per minute through twotypes of test cartridge filters. Test cartridges were Parker FulfloPoly-Mate (#PM600-10AE-DO) and Parker Fulflo Glass-Mate(#PMG400-10FE-DO) filters. Filters were utilized in testing as untreated(as received) or treated with a quaternary ammonium organosilanecompound marketed under the tradename Z71 by Zoono of New Zealand(Coating Systems Laboratories, Inc., EPA Reg. No. 008007-1,3-trimethoxysilyl propyl dimethyl octadecyl ammonium choride) solutionthrough immersion and oven drying at 120° C. Flow rates were measuredutilizing PVDF Flowmeter/Totalizer (GPI, Great Plains Industries)calibrated for flow rates of 1.2-12.0 gallon per minute. Microbialtesting was performed using a Hygiena ATP meter in conjunction withHygiena Aquasnaps (#AQ-100). A test apparatus was assembled and testingperformed for four filter systems. Filter system A consisted ofuntreated Poly-Mate filter. Filter system B consisted of Z71 treatedPoly-Mate cartridge filter. Filter system C contained the untreatedGlass-Mate cartridge and Filter system D contained the Z71 treatedGlass-Mate cartridge. The units were assembled individually by placingeach designated filter system into the cartridge holder within the testapparatus. The assembled units were tested individual at a flow rate of1.0-1.2 gpm. Initial microbial count of the San Diego seawater beforetesting was measured at 720 utilizing Hygiena test meter and HygienaAquasanp. Results of the testing using the four systems are summarizedin Table 1:

TABLE 1 Initial Microbial Count After Filter System Count FiltrationReduction (%) A 720 646 10.3 B 720 12 98.3 C 720 664 7.8 D 720 6 99.1

As can be observed, filter systems B and D that were coated with aquaternary ammonium organosilane material achieved a greater than 95%reduction in microbes through only one pass through the filter.

In places where the description above refers to particularimplementations of ballast water treatment systems and implementingcomponents, sub-components, methods and sub-methods, it should bereadily apparent that a number of modifications may be made withoutdeparting from the spirit thereof and that these implementations,implementing components, sub-components, methods and sub-methods may beapplied to other ballast water treatment systems. For example, thefeatures of the reagents of the various implementations are equallyapplicable to the coatings of the implementations described herein.

What is claimed is:
 1. A ballast water treatment system comprising: aballast water intake pump coupled to the intake screen and adapted todraw untreated water in through the intake screen; a particulate filtersystem coupled to the screen filter and with one or more ballast tanksconfigured to be coupled to the ship, the particulate filter systemcomprising particles 0.6 mm to 6 mm in length; a ballast water dump pumpcoupled with the one or more ballast tanks and adapted to draw outtreated water stored in the one or more ballast tanks and discharge itback to the body of water surrounding the ship; wherein the particulatefilter system comprises particles comprising a quaternary organosilanecoating produced from a quaternary ammonium organosilane reagent havingthe formula:

wherein A is a member independently selected from the group consistingof —OR⁴, substituted or unsubstituted alkyl, substituted orunsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted heterocycloalkyl, substituted orunsubstituted aryl, and substituted or unsubstituted heteroaryl; andwherein R⁴ is a member selected from the group consisting of hydrogen,substituted or unsubstituted alkyl, substituted or unsubstitutedheteroalkyl, substituted or unsubstituted cycloalkyl, substituted orunsubstituted heterocycloalkyl, substituted or unsubstituted aryl, andsubstituted or unsubstituted heteroaryl; and R is substituted orunsubstituted alkylene; R¹, R², and R³ are members each independentlyselected from the group consisting of hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted heteroalkyl,substituted or unsubstituted cycloalkyl, substituted or unsubstitutedheterocycloalkyl, substituted or unsubstituted aryl; and substituted orunsubstituted heteroaryl; Z is a member selected from the groupconsisting of fluoride, chloride, bromide, iodide, tosylate, hydroxide,sulfate, and phosphate; and n is 1, 2, or
 3. 2. The system of claim 1,wherein the body of water comprising microorganisms is one of salt waterand fresh water.
 3. The system of claim 1, further comprising arecirculation pump coupled with the one or more ballast water tanks, therecirculation pump coupled with a recirculation filter comprisingparticles 0.6 mm to 6 mm in length coated with the quaternaryorganosilane coating, the recirculation pump adapted to draw treatedwater from the one or more ballast water tanks through the recirculationfilter and back into the one or more ballast water tanks.
 4. The systemof claim 1, wherein the one or more ballast water tanks further comprisean open-celled foam coated with the quaternary organosilane coating. 5.The system of claim 4, wherein the open-celled foam comprises a materialselected from the group consisting of polymeric materials, stainlesssteel, copper, silicon, carbon, and silicon carbide.
 6. The system ofclaim 4, wherein the open-celled foam comprises a range of pores perinch (PPI) between 10 PPI and 110 PPI.
 7. The system of claim 4, whereinthe open-celled foam comprises a surface area per gram less than asurface area per gram of one of filter sand and zeolite.
 8. The systemof claim 1, wherein a surface of the one or more ballast tanks is coatedwith the quaternary organosilane coating.
 9. The system of claim 1,wherein the quaternary ammonium organosilane reagent comprises one ofTetradecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;Octadecyldimethyl(3-trimethoxysilylpropyl)ammonium chloride;Didecylmethyl-N-(3-trimethoxysilylpropyl)ammonium chloride; and anycombination thereof.
 10. A ballast water treatment system comprising: aballast water intake pump coupled to the intake screen and adapted todraw untreated water in through the intake screen; a particulate filtersystem coupled to the screen filter and with one or more ballast tanksconfigured to be coupled to the ship, the particulate filter systemcomprising particles 0.6 mm-6 mm in length; a ballast water dump pumpcoupled with the one or more ballast tanks and adapted to draw outtreated water stored in the one or more ballast tanks and discharge itback to the body of water surrounding the ship; wherein the particulatefilter system comprises particles comprising a quaternary organosilanecoating produced from a quaternary ammonium organosilane reagent havingthe formula:A_(4-n)Si(R NHaR¹ _(b) Z)_(n) wherein A is a member selected from thegroup consisting of alkoxy radicals of 1 to 8 carbon atoms, alkyletheralkoxy radicals of 2 to 10 carbon atoms, and alkyl radicals with 1 to 4carbon atoms; R is a divalent hydrocarbon radical with 1 to 8 carbonatoms; R¹ is a member selected from the group consisting of alkylradicals with 1 to 12 carbon atoms, alkyl ether hydrocarbon radicals of2 to 12 carbon atoms, hydroxy-containing alkyl radicals of 1 to 10carbon atoms, and nitrogen-containing hydrocarbon radicals of 1 to 10carbon atoms, wherein the nitrogen atom has three bonds; a is 0, 1, or2; b is 1, 2 or 3; and the sum of a and b is 3; Z is a member selectedfrom the group consisting of chloride, bromide, iodide, tosylate,hydroxide, sulfate, and phosphate; and n is 1, 2 or
 3. 11. The system ofclaim 10, wherein the body of water comprising microorganisms is one ofsalt water and fresh water.
 12. The system of claim 10, furthercomprising a recirculation pump coupled with the one or more ballastwater tanks, the recirculation pump coupled with a recirculation filtercomprising particles 0.6 mm to 6 mm in length coated with the quaternaryorganosilane coating, the recirculation pump adapted to draw treatedwater from the one or more ballast water tanks through the recirculationfilter and back into the one or more ballast water tanks.
 13. The systemof claim 10, wherein the one or more ballast water tanks furthercomprise an open-celled foam coated with the quaternary organosilanecoating.
 14. The system of claim 13, wherein the open-celled foamcomprises a material selected from the group consisting of polymericmaterials, stainless steel, copper, silicon, carbon, and siliconcarbide.
 15. The system of claim 13, wherein the open-celled foamcomprises a range of pores per inch (PPI) between 10 PPI and 110 PPI.16. The system of claim 13, wherein the open-celled foam comprises asurface area per gram less than a surface area per gram of one of filtersand and zeolite.
 17. The system of claim 10, wherein a surface of theone or more ballast tanks is coated with the quaternary organosilanecoating.
 18. A ballast water treatment system comprising: a ballastwater intake pump coupled to the intake screen; a particulate filtersystem coupled to the screen filter and with one or more ballast tanks,the particulate filter system comprising particles 0.6 mm-6 mm inlength; a ballast water dump pump coupled with the one or more ballasttanks; wherein the multi-cartridge filter system comprises two or morecartridge filters comprising a quaternary organosilane coating producedfrom a quaternary ammonium organosilane reagent having the formula:

wherein A is a member independently selected from the group consistingof —OR⁴, substituted or unsubstituted alkyl, substituted orunsubstituted heteroalkyl, substituted or unsubstituted cycloalkyl,substituted or unsubstituted heterocycloalkyl, substituted orunsubstituted aryl, and substituted or unsubstituted heteroaryl; andwherein R⁴ is a member selected from the group consisting of hydrogen,substituted or unsubstituted alkyl, substituted or unsubstitutedheteroalkyl, substituted or unsubstituted cycloalkyl, substituted orunsubstituted heterocycloalkyl, substituted or unsubstituted aryl, andsubstituted or unsubstituted heteroaryl; and R is substituted orunsubstituted alkylene; R¹, R², and R³ are members each independentlyselected from the group consisting of hydrogen, substituted orunsubstituted alkyl, substituted or unsubstituted heteroalkyl,substituted or unsubstituted cycloalkyl, substituted or unsubstitutedheterocycloalkyl, substituted or unsubstituted aryl; and substituted orunsubstituted heteroaryl; Z is a member selected from the groupconsisting of fluoride, chloride, bromide, iodide, tosylate, hydroxide,sulfate, and phosphate; and n is 1, 2, or 3; and wherein the ballastwater treatment system is adapted to receive untreated water via theintake screen from a body of sea water comprising microorganisms andachieve at least a 95% reduction in a number of the microorganisms inthe untreated water after a single pass through the particulate filtersystem.